1-chloro-1, 2, 3, 4, 4-pentafluoro-1, 3-butadiene



United States Patent 1-CHLORO-1,2,3,4,4-PENTAFLUORO-1,3- BUTADIENE Robert P. Ruh and Ralph A. Davis, Midland, Mich, as-

signors to The Dow Chemical Company, Midland, Mich., a corporation of Delaware No Drawing. Application June 24, 1953, Serial No. 363,949

1 Claim. (Cl. 260-653) This invention concerns a new compound, l-chloro- 1,2,3,4,4-pentafi.uoro-1,3-butadiene, and a method for its preparation.

This compound, CFCl=CF-CF=CF2, is a low boiling, nonflammable liquid which exhibits strong parasiticidal activity against fungi, bacteria, and insects. It is surprisingly effective in the fumigation of grains for the control of such insects as the confused flour beetle, the black carpet beetle, and the granary weevil. This new chlorofluorobutadiene may also be polymerized to give high molecular weight rubbery polymers which are stable against heat and oxidation.

According to the process of the invention,

is prepared by the dechlorination of l,1,2,3,4-pentachloro-1,2,3,4,4-pentafluorobutane,

with zinc in the presence of a lower alkanol under essentially anhydrous conditions. The alkanols which may advantageously be employed in the instant process are those having less than six carbon atoms per molecule, such as methanol, ethanol, isopropanol, sec-butanol, etc. Usually CFCl2CFClCFCl-CF2C1 is dissolved in an equal volume of absolute ethanol and added gradually to a slurry of powdered zinc in absolute ethanol. A sufiiciently large amount of zinc to remove four chlorine atoms from each molecule of the chlorofluorobutane is generally employed, e. g. slightly greater than two atomic proportions of zinc per molecular proportion of CFCl2CFClCFClCF2Cl. The dechlorination reaction is highly exothermic and may be represented by the following equation:

The reaction may be carried out in a glass flask or ceramic-lined vessel equipped with a water-cooled reflux condenser. Although the reaction will proceed readily at C., the temperature at which the reaction is generally conducted is conveniently the reflux temperature of the reaction mixture, viz. approximately 80 C. when ethanol is the alcoholic solvent. The rate at which the l-chloro-1,2,3,4-4-pentafluoro-l,3-butadiene product is formed is roughly proportional to the rate of addition of the chlorofluorobutane reactant, i. e. dechlorination occurs almost instantaneously upon bringing the reactants into contact. Upon adding all the chlorofluorobutane, the reaction mixture is heated for a short period of time to insure essentially complete reaction. The organic product is thereafter usually washed with water to remove alcohol and zinc chloride, dried, e. g. with anhydrous calcium chloride, and fractionally distilled to separate the CFCl=CF-CF=CF2.

2,745,835 Patented May 15, 1956 ice 2 The following example illustrates the process of the invention, but is not to be construed as limitative:

Example l-chloro-l,2,3,4,4-pentafluoro-1,3-butadiene was prepared by the dechlorination of 1,1,2,3,'4-pentachloro- 1,2,3,4,4-pentafluorobutane according to the procedure hereinafter described:

The l,1,2,3,4 pentachloro 1,2,3,4,4 pentafluorobutane starting material employed in the dechlorination reaction was prepared by the fluorination of the known compound 1,1,2,3,4,4 hexachloro l,2,3,4 tetrafluorobutane. The fluorination reaction was carried out by heating l,1,2,3,4,4 hexachloro 1,2,3,4 tetrafluorobutane and a slightly greater than theoretical proportion of SbClzFa in a closed reaction vessel at a temperature of about 250 C. for a period of several hours. Thereafter, the reaction product was cooled, washed with water, and dried. The dry organic product so obtained was fractionally distilled to separate 1,l,2,3,4-pentachloro- 1,2,3,4,4-pentafluorobutane,

boiling at 168 C. at 739 mm. Hg absolute. This material was employed to prepare 1-chloro-l,2,3,4,4-pentafluoro-1,3-butadiene, CFCI=CFCF=CF2, as described below:

Into a 2-liter glass flask equipped with a dropping funnel, water-cooled reflux condenser, and mechanical stirring device were charged 317 grams (4.84 moles) of powdered zinc and ml. of absolute ethanol. Thereafter 708 grams (2.2 moles) of dissolved in an equal volume of absolute ethanol was gradually added to the reaction flask during a period of 3 hours at a rate such as to maintain a steady reflux of the absolute ethanol. When all of the alcoholic solution of CFCl2CFClCFCl-CF2C1 had been added to the flask, 275 ml. of additional ethanol was added and the reaction mixture was heated under reflux for eight hours longer. The reaction product was then cooled, washed with water, and dried over C3504. Fractional distillation of the dry product gave the following fractions: 197 grams of crude CFC1=CFCF=CF2 boiling from 35 to 42.5 C. at 745 mm. Hg abs., 56 grams of C4CI3F5 fraction boiling from 96 to 100.5 C. at 748 mm. Hg abs., and 30 grams of recovered starting material, CFCl2CFC1CFCl-CF2C1. Based on the total moles of CFClzCFClCFCl-CF2C1 employed in the dechlorination reaction, the conversion to CFCI=OFCFCF: Observed Theory Carbon 24. 28 26. 89 Chlorine 19. 45 19. 89 Fluorine 52. 9 53. 22

The 1 chloro 1,2,3,4,4 pentafluoro 1,3 butadiene prepared as above was tested as a fumigant by exposing a considerable number of black carpet beetle larvae and confused flour beetle adults to the vapors of this compound. The fumigation was carried out for a That which is claimed is:

period of 16 hours in a closed chamber at a temperature 1 Chlofo 1,2,3,4,4 Pentafllloro blltadiefle- Of fibOllt 25 and at a concentration Of POE-11d Of References Cited inthe file of this atent 1 b 1tad1ene P 5 Preparation, Properties and Technology of Fluorine 1000 cubic feet of space. As a result of this operation, and Organic Fl i C mpounds, Slesser and Schram,

a 100% kill of both species of insects was obtained. page 670 (#33) (1950). 

